Method and composition for waterproofing

ABSTRACT

A method and composition for waterproofing a substrate includes applying a coating composition to a surface of the structural unit. The coating composition includes a) an organic solvent, b) a hydrocarbon resin and c) a copolymer having styrene and diene monomer units, a polymer having olefin monomer units, or a copolymer having styrene and olefin monomer units, or mixtures thereof.

RELATED APPLICATIONS

This is a continuation of U.S. Ser. No. 09/476,833, filed Jan. 3, 2000now U.S. Pat. No. 6,230,452, which is a divisional of U.S. Ser. No.09/274,180, filed Mar. 23, 1999, now U.S. Pat. No. 6,025,032, which is acontinuation-in-part of U.S. Ser. No. 09/034,538, filed Mar. 3, 1998 nowabandoned, which applications are expressly incorporated herein.

FIELD OF THE INVENTION

The present invention relates to a method and a polymeric compositionfor waterproofing. More particularly, the present invention relates to amethod and composition using a hydrocarbon resin and a polymer havingeither one styrene-containing polymer or one olefin-containing polymeror a mixture of these polymers to waterproof.

BACKGROUND OF THE INVENTION

Structures used in construction, such as foundations and walls, includematerials, such as masonry, cement, wood, plaster, stone, clay or brickthat may be porous. Such porous materials can be degraded by waterand/or loss of water from the porous materials. Below grade structuresare often subjected to hydrostatic pressure from ground water. Abovegrade structures are subject to precipitation and water from othersources. A variety of methods and products for waterproofing and/orsealing these structures against outside water have been developed.

One type of waterproofing and/or sealing system includes polyvinyl orpolyethylene sheeting adhered or fastened to the surface of thestructure. If an adhesive is used to adhere the sheeting to thestructure, the adhesive may not stick well due to dust (e.g., cement orstone dust) produced during construction and other activities and loseits adhesion over time. On the other hand, if fasteners, such as nailsor staples, are used to attach the sheeting to the structure, thefasteners typically puncture the sheeting and the structure beneath,providing a channel through which water can flow. Moreover, there areseams between the sheets that require the use of a fastener or adhesiveto close. The adhesive may be attacked by microorganisms and/oroxidation and degraded or may dissolve in water over time, allowingwater to flow through the seam. Fasteners puncture the sheeting andallow water through the resulting holes. In addition, the waterproofingsheets are often difficult to form around non-uniform structures andadverse weather conditions may hinder the placement of the sheets on thestructure. For example, wind may cause wrinkles in the sheet as it ispositioned on the structure and, on very cold days, the sheets may tearor even shatter during installation.

Another type of waterproofing and/or sealing system includes theapplication of a coating composition on the structure. One common typeof coating composition for waterproofing and sealing is tar- orasphalt-based. Although these compositions are relatively inexpensiveand can be applied year-round, the materials in the composition oftenleach away from the wall. This often contaminates the soil and reducesthe amount of protection afforded by the coating. Moreover, thesecompositions typically contain a large amount of organic material whichmay be attacked by soil- or water-borne microorganisms, thereby reducingthe effectiveness of the coating.

Other types of coating compositions have been developed. Many of thesecoating compositions, however, do not produce a durable film over poroussubstrates (e.g., cement, masonry blocks, wood, etc.). Often, the filmthat is formed using these coating compositions is easily puncturedand/or includes components that are degradable or leach away from thefilm thus losing its adhesion to substrates. These coating compositionsneed to be applied with a significant amount of volatile organiccompounds as solvents. These emitted volatile organic compounds (VOCs)are limited by current environmental regulations. Moreover, a number ofthe coating compositions are difficult to apply and/or relativelyexpensive.

There is a need for alternative waterproofing and/or sealingcompositions which emit less volatile organic compounds uponapplication, are durable, flexible, and stable in below grade and abovegrade applications. Such compositions may also be useful for coatingother substrates, as well.

SUMMARY OF THE INVENTION

The present invention relates to methods and compositions forwaterproofing and sealing a surface of a substrate. One embodiment is amethod of coating a surface of a substrate. The method includes applyinga coating composition to the surface of the substrate. The coatingcomposition includes a) an organic solvent, b) a hydrocarbon resin andc) a copolymer having styrene and diene monomer units with astyrene-content of less than 60 wt. %, a polymer having olefin monomerunits, a copolymer having styrene and olefin monomer units with astyrene content of less than 60%. wt, or mixtures thereof.

A further embodiment is a method of a method of coating a surface of asubstrate. This method includes applying a coating composition to thesurface of the substrate. The coating composition includes: a) anorganic solvent, b) about 25 to 85 phr of a coumarone-indene polymer andc) about 15 to 75 phr of a copolymer having styrene and diene monomerunits with a styrene-content of more than 5 wt. % and less than 60 wt.%, a copolymer having olefin and styrene monomer units with astyrene-content of about 60 wt. % or less, or mixtures thereof.

Another embodiment is a method of applying a waterproofing coating to astructural unit. A coating composition is applied to a surface of thestructural unit. The coating composition includes; a) about 20 to 400phr of an organic solvent, b) about 1 to 66 phr of a coumarone-indenepolymer, c) about 34 to 99 phr of a styrene-diene block copolymer havinga styrene-content of about 10 to 35 wt. %, a polyolefin homopolymer, astyrene-olefin block copolymer with a styrene-content of about 10 to 60wt. % or mixtures thereof and d) about 20 to 600 phr of a filler. Thecoating composition is then dried to form a film.

A further embodiment of the invention is a waterproofing composition.The waterproofing composition includes; a) about 33 phr to about 250 phrof an organic solvent, b) about 10 to 50 phr of a coumarone-indenepolymer; c) about 50 to 90 phr of a copolymer having styrene and dienemonomer units with a styrene-content greater than 5 wt. % and less than60 wt. %, a polymer having olefin monomer units, a copolymer havingstyrene and olefin monomer units with a styrene content of about 10 to60 wt. % or mixtures thereof.

Yet another embodiment of the invention is a waterproofing composition.The waterproofing composition includes; a) about 50 to about 150 phr ofan organic solvent, b) about 10 to 30 phr of a coumarone-indene polymer,c) about 45 to 80 phr of a polymer having styrene and diene monomerunits with a styrene-content of about 10 to 35 wt. %, and d) about 10 to25 phr of a polymer having olefin monomer units and a styrene-content ofabout 10 to 60 wt. % .

The above summary of the present invention is not intended to describeeach disclosed embodiment or every implementation of the presentinvention. The detailed description which follows more particularlyexemplify these embodiments, but do not limit the scope of theinvention, as defined by the claims.

DESCRIPTION OF THE PREFERRED EMBODIMENT

The present invention is believed to be applicable to methods andcoating compositions for waterproofing and/or sealing a surface of asubstrate. In particular, the present invention is directed to methodsand coating compositions using a combination of a) a hydrocarbon resinand b) one or more polymers having styrene and usually, but notnecessarily, diene monomer units or one or more polymers having olefinmonomer units or mixtures of these polymers. While the present inventionmay not be so limited, an appreciation of various aspects of theinvention will be gained through a discussion of the examples providedbelow.

The term “polymer” includes homopolymers and copolymers, unlessotherwise indicated.

The term “hydrocarbon resin” is a term that is used to describe a lowmolecular weight thermoplastic polymer synthesized via the thermal orcatalytic polymerization of coal-tar fractions, cracked petroleumdistillates, terpenes, or pure olefinic monomers.

The term “monomer unit” indicates a unit of a polymer which is derivedfrom or has the same chemical structure as a unit derived from aparticular monomer.

The term “phr”, as used herein, is a unit of measurement which indicatesthe number of parts by weight of a particular component in a coatingcomposition having 100 parts by weight of a polymeric binder resin.

The term “substrate” includes any surface that is capable of beingcoated with the composition of the invention.

A preferred substrate is a “structural unit.” The term “structuralunits” includes, by way of example, foundations, basement walls,retaining walls, cement posts, other building walls, dry wall, poolenclosures, tub and shower enclosures, highway structures (e.g., postsand walls), wooden or metal fence posts, sheet rock, plywood, waferboard, wall sheeting, pressed board, containment basins and walls,fabricated walls, floor panels, roofs, plaza decks, decks, floors,concrete, pre-stressed concrete other substrates that are buried or areexposed to water or weathering conditions, and the like. Thesestructural units are typically made from masonry, cement, wood, plaster,stone, gypsum, clay, brick, tile, terra cotta, cardboard, paper, and thelike.

A coating composition for waterproofing or sealing a structural unit orany other substrate has a polymeric binder resin in an organic solvent.In addition, the coating composition may optionally have a filler, apigment or dye, and/or a plasticizer. Other optional components of thecoating composition include, for example, an antioxidant, a UV(ultraviolet) absorber or blocker, an ozone blocker, a foaming agent, atackifier, a perfume, and/or a deodorizer. Typically, the coatingcomposition includes 100 parts by weight of a polymeric binder resin,about 20 to 400 phr of an organic solvent, 0 to about 600 phr of afiller, 0 to about 10 phr of a pigment or dye, and 0 to about 50 phr ofa plasticizer. Other optional components of the coating composition aretypically available in amounts ranging from 0 to about 10 phr.

The polymeric binder resin is a combination of (a) a hydrocarbon resinand (b) one or more polymers having styrene and usually, but notnecessarily, diene monomer units or one or more polymers having olefinmonomer units or mixtures of these polymers. The components of thebinder resin are chosen based on the desired properties of thecomposition and resulting film.

The use of a hydrocarbon resin component in the polymeric binder resinis cost efficient by reducing the required amount of more costlypolymeric components in the polymeric binder composition. The use of thehydrocarbon resin also reduces the amount of volatile organic components(VOCs) needed in the composition. This reduction of solvent directlylowers VOC emissions during all stages of the production, storage andapplication process of the coating composition. The hydrocarbon resinfurther improves the processability of the polymeric binder resin bylowering the overall molecular weight and viscosity of the resin. Thelower viscosity aids in the application of the resin to the substrate.The use of a hydrocarbon resin also improves the flexoral modulus, andgives lower gas and vapor permeation rates to the resulting film. Thehydrocarbon resin enhances the adhesive and elongation properties of thecomposition and resulting film. The resulting film is a non-tacky,flexible, and tough coating. The hydrocarbon resin also promotescompatibility of the components in the composition.

The styrene component of the polymeric binder resin provides hardnessand durability to a film formed from the coating composition. The dienecomponent increases the flexibility and the impact resistance of theresulting film. The olefin component gives the film increased elasticityand resistance to oxidation and degradation due to, for example,ultraviolet light, ozone, and other chemical agents in the atmosphere orsoil.

Hydrocarbon Resin

Hydrocarbon resins used in accordance with the invention are lowmolecular weight polymers (oligomers) produced from by-producthydrocarbon, petroleum or coal tar streams. Polymerization is carriedout using any one of a number of acid catalysts or as a free radicalreaction using heat and pressure. The hydrocarbon resins include bothnatural and synthetic types; aliphatic and aromatic. Preferredhydrocarbon resins include coumarone-indene resins. Molecular weights ofthe hydrocarbon resins range from about 200 up to about 2000, andpreferably range from about 350 to about 1000.

Coumarone-indene resins (polymers) suitable for use in the blends ofthis invention generally can include those resins obtained throughcatalytic polymerization of coal-tar naphthas. Although named after twoparticular components of these resins, coumarone (I) and indene (II),these resins are actually produced by the cationic polymerization ofpredominantly aromatic feedstocks. These feedstocks, such as, coal-tarnaphthas contain resin-forming materials, for example, styrene,coumarone, indene, methyl coumarones, methyl indenes,dimethylcoumarones, dicyclopentadiene, methyl cyclopentadienes,cyclohexadienes, naphthalene, and anthracene derivatives.

Polymerization of these resin-forming materials is effected by thecatalytic action of a Bronsted acid, such as sulfuric acid or aderivative thereof, or of a Lewis acid, such as stannic chloride,antimony pentachloride, aluminum chloride, titanium tetrachloride, orboron trifluoride, on the coal tar naphthas. The polymers, generally,are not homopolymers, but are derived from mixtures of severalresin-forming materials. The polymers may also be condensed with phenoland derivatives thereof, or with lower aliphatic aldehydes such asformaldehyde, or may be hydrogenated to remove residual unsaturation.Such hydrocarbon resins are commercially available and include, forexample, polyindenes, polycoumarones, coumarone-indene polymers,phenol-modified coumarone-indene polymers, coumarone-indene-styrenepolymers, styrene-cyclopentadiene polymers, styrene-indene polymers,dicyclopentadiene resins, terpene resins, naphthalenic resins,anthracenic resins, lignin and the like.

The most preferred hydrocarbon resins are commercially availablemodified coumarone-indene polymers including, for example, Nevex 100®and Cumar® from Neville Chemical Company. Vantack® 85, 95 and 105 seriesresins from Vanderbilt Chemical Co., may also be used.

Polymers

The polymer typically includes a combination of up to three types ofpolymers. These three types include a) styrene-diene copolymers having astyrene content less than 60 wt. % and typically ranges from about 5 to60 wt. % and, preferably, from about 10 to 35 wt. %, b) polyolefins, andc) styrene-olefin copolymers having a styrene content less than 60 wt. %and typically ranges from about 10 to 60 wt. % and preferably, fromabout 20 to 50 wt. %. A high styrene-content polymer, such as a styrenehomopolymer or copolymer having a styrene content of 60 wt. % or greatermay optionally be added to least one of the above polymer or polymers.The combination of polymers are typically chosen to produce a durablefilm with elastomeric properties. Typically these films contain lessthan 60 wt % styrene thus, these films are durable while remainingelastic. These films typically contain significantly less styrene, andare more elastic than films made from the coating compositions describedin U.S. Pat. No. 5,482,737.

The amounts of each type of polymer in the polymeric binder resin may berepresentative of a single polymer or copolymer or a combination ofpolymers and/or copolymers. The polymers used in the polymeric binderresin may be virgin polymers, reground polymers, recycled polymers, ormixtures thereof.

Typical diene monomer units include butadiene and isoprene. Butadiene isthe preferred diene monomer unit. Typical olefin monomer units includeethylene, propylene, butylene (i.e., 1-butene and isomers), andisobutylene (i.e., isobutene). Preferred olefin monomer units includeethylene, butylene, and isobutylene.

The polymeric binder resin often includes at least one styrene-dienecopolymer. One example of a suitable styrene-diene copolymer is astyrene-diene-styrene triblock copolymer which has two endblocks ofpolymerized styrene monomer units separated by a central block ofpolymerized diene monomer units. Suitable triblock polymers include, forexample, styrene-butadiene-styrene (S-B-S) polymers andstyrene-isoprene-styrene (S-I-S) polymers. Commercial S-B-S and S-I-Spolymers include, for example, many of the Kraton® D 1100 Seriespolymers from Shell Chemical Company (Houston, Tex.) and Stereon® BlockCopolymers from Firestone Synthetic Rubber & Latex Co. (Akron, Ohio).For example, Kraton® D 1101 and D 1102 are S-B-S polymers and Kraton® D1107 is an S-I-S polymer. These copolymers typically have astyrene-content of about 5 to 60 wt % and usually about 10 to 35 wt %.

Another example of a suitable styrene-diene copolymer is a styrene-dienediblock polymer, such as a styrene-butadiene (S-B) copolymer or astyrene-isoprene (S-I) copolymer. Commercially available triblockpolymers often include at least some diblock polymer.

The styrene-diene copolymer portion of the polymeric binder resintypically includes at least one block copolymer. Random copolymers mayalso be used, particularly in combination with a block copolymer orcopolymers.

The polymeric binder resin often includes at least one polyolefin.Suitable examples of polyolefins include polyethylene, polypropylene,and polybutene. Preferred polyolefin include polyethylene, polybutene,polyisobutylene, and polymers having a combination of butylene andisobutylene monomer units (e.g., a polymer having about 25 to 30 wt. %isobutylene monomer units and about 70 to 75 wt. % butylene monomerunits). Polyolefins may be obtained from a variety of manufacturers anddistributors.

The polymeric binder resin often includes at least one styrene-olefincopolymer with a typical styrene-content less than 60 wt. % andpreferably ranging from about 10 to 60 wt. %, and more preferably, about20 to 50 wt. %. Such copolymers combine the hardness of the styrenemonomer units with the elastomeric properties of the olefin monomerunits. The styrene-olefin copolymer portion of the polymeric binderresin typically includes at least one block copolymer, however, randomcopolymers may also be used, particularly in combination with blockcopolymers. Examples of styrene-olefin copolymers includestyrene-ethylene-butylene-styrene (S-EB-S) block copolymers,styrene-ethylene-propylene-styrene (S-EP-S) block copolymers,styrene-ethylene-butylene (S-EB) block copolymers, andstyrene-ethylene-propylene (S-EP) block copolymers. Examples of thesecopolymers include Kraton® G 1600 and 1700 series polymers and Kraton®FG 1900 series polymers. A preferred polymer of this type is thestyrene-ethylene-butylene-styrene polymer, such as, for example, many ofthe Kraton® G 1600 Series polymers, including Kraton® G 1650 and 1652polymers.

The polymeric binder resin may include a polymer having a relativelyhigh styrene-content. The high-styrene content polymer may increase thehardness and durability of a film formed from the coating composition.This high styrene-content polymer may be styrene homopolymer or acopolymer of styrene with, for example, one or more diene, olefin,acrylonitrile, and/or acrylate monomer units. Suitable highstyrene-content polymers include, for example, polystyrene homopolymer,high impact polystyrene (HIPS), and medium impact polystyrene (MIPS).Both HIPS and MIPS are often copolymers of styrene and a diene, such asbutadiene. HIPS and MIPS typically have a styrene content that rangesfrom 60 wt. % to 99 wt. %.

The impact resistance of films formed using coating compositions havinghigh styrene-content polymers typically increases as the overall dienecontent increases. The diene content of the coating composition may bemodified, for example, by using a polymer with higher diene-content ordecreasing the amount of the high styrene-content polymer in thepolymeric binder resin. The impact resistance of the film may also bemodified by the addition of a plasticizer. On the other hand, thehardness of films formed using these polymers typically decreases as thediene content increases. Thus, the desired properties of the film may betailored by varying the polymeric binder resin composition.

In one embodiment of the invention, the polymeric binder resin includes:a) about 25 to 85 phr hydrocarbon resin: b) about 15 to 75 phr of acopolymer having styrene and diene monomer units with a styrene-contentof about 5 to 60 wt. %, a copolymer having olefin and styrene monomerunits with a styrene content of about 60 wt. % or less, or mixturethereof.

In another embodiment of the invention, the polymeric binder resinincludes: a) about 1 to 66 phr, preferably about 10 to 50 phrcoumarone-indene polymer; b) about 34 to 99 phr, preferably about 50 to90 phr of a copolymer having styrene and diene monomer units with astyrene-content of about 5 to 60 wt. % and preferably 10 to 35 wt. %, apolymer having olefin monomer units, a copolymer having styrene andolefin monomer units with a styrene content of about 10 to 60 wt. % andmixtures thereof.

In another embodiment of the invention, the polymeric binder resinincludes: a) about 10 to 30 phr coumarone-indene polymer; b) about 45 to80 phr of a polymer having styrene and diene monomer units with astyrene-content of about 10 to 35 wt. %; and c) about 10 to 25 phr of apolymer having olefin monomer units and a styrene-content of about 10 to60 wt. %.

Solvent

The polymers and hydrocarbon resins that form the polymeric binder resinare dissolved and/or dispersed in an organic solvent to form a coatingcomposition. The amount of solvent used determines the drying time, andappropriate method of application for the coating composition. A varietyof solvents may be used. Suitable solvents which are commonly usedinclude, for example, aromatic hydrocarbons, cycloaliphatichydrocarbons, terpenes, unsaturated hydrocarbons, organic carbonates,and halogenated aliphatic and aromatic hydrocarbons. Suitable solventsinclude toluene, xylene, benzene, halogenated benzene derivatives, ethylbenzene, mineral spirits, naphtha, cyclohexane, methylene chloride,ethylene chloride, trichlorethane, chlorobenzene, propylene, ethylenecarbonate, nitropropane, acetone, ethyl acetate, propyl acetate, butylacetate, and isobutyl isobutyrate. Preferred solvents are aromatichydrocarbons, such as toluene, xylene, benzene, and halogenated benzenederivatives, as well as mineral spirits.

For environmental reasons, it is desirable to usc as little solvent aspossible in the coating composition. The lower limit on the amount ofsolvent may be determined by the amount of solvent needed to solvateand/or disperse the components of the coating composition. If too littlesolvent is used, then the coating composition may be too viscous for theparticular application. On the other hand, if too much solvent is used,the coating composition may not have the necessary viscosity to ensurethat a proper coating is deposited on the structural unit and anexcessive amount of VOCs are emitted into the environment. This canresult in a film that may be thin, easily punctured, and/or have anunacceptable amount of pinholing. In addition to the use of a solvent,the viscosity of a coating composition may often be reduced by warmingthe coating composition. Surprisingly, the addition of hydrocarbonresins to the composition reduces the amount of solvent needed tosolvate and/or disperse the components of the coating composition.

The use of the hydrocarbon resin reduces the amount of solvent orvolatile organic components (VOCs) needed in the composition for aspecified final film thickness. Coating a set area with a specified filmthickness emits less VOCs with the hydrocarbon resin included in thecoating composition than without the hydrocarbon resin in the coatingcomposition. This reduction of solvent directly lowers VOC emissionsduring application of the coating composition to a substrate. Lowersolvent emissions during application of the coating composition is asurprising benefit gained by using a hydrocarbon resin in the coatingcomposition.

The desired viscosity of the coating composition often depends on themethod of application of the coating composition. Coating compositionsthat are formulated for application using a brush or roller can often bemore viscous than those formulated for spraying. The desired viscositymay also depend on whether the surface to be coated is a verticalsurface, where a less viscous coating composition may run, or ahorizontal surface.

The amount of solvent in the coating composition typically ranges fromabout 20 to 400 phr, preferably from about 33 to 250 phr, and morepreferably from about 50 to 150 phr, based on 100 part by weight of thepolymeric binder resin. However, larger or smaller amounts of solventmay be used depending on the desired composition and viscosity of thecoating composition.

Optional Components

The coating composition typically includes a filler. The filler mayincrease the strength of the coating composition and/or replace costlymaterials of the polymeric binder resin. The filler may also modify thephysical properties of the coating composition and films formed usingthe coating composition, including, for example, the color, opacity,affinity for other coatings, density, rheology, stiffness, and modulusof the coating composition and/or film. Any particular filler may haveone or more of these, or other, functions in the coating composition.

In addition, a coating composition with a filler may more easily andreliably cover holes, depressions, recesses, cracks, and crevices in asubstrate, for example, in masonry blocks, concrete, wood, and otherporous or rough substrates. The presence of a filler may reduce the sizeand number of pinholes in a film formed from the coating composition.These pinholes arise, at least in some cases, because of gravity and/orcapillary action that draws the coating composition into the hole,depression, recess, crack, or crevice in the substrate, creating a breakor pinhole in the resulting film. The filler often includes particlesthat, because of their larger size, provide structural support that, incombination with the polymeric binder resin, forms a film across thehole, depression, recess, crack, or crevice. This reduces the tendencyto form pinholes.

Surprisingly, the use of a hydrocarbon resin also increases the amountof filler that can be added to the coating composition.

Suitable fillers include, for example, carbonates, clays, talcs, silicasincluding fumed silica and amorphous silica, silico-aluminates, aluminumhydrate, metal oxides (e.g., oxides of aluminum, iron, zinc, magnesium,and titanium), silicates (e.g., mica), sand, Portland cement, carbonfilaments, glass, fiberglass, cellulose, graphite, mortar powder,calcium carbonate, sulfates (such as magnesium or calcium sulfates), andthe like. Additional suitable fillers include, for example, polymericmaterials such as vinyl and other rubbers, nylon, rayon, polyesters, andthe like, as well as combinations thereof, particularly combinations ofrubber and the other components. These polymeric materials may bevirgin, reground or recycled and may include pellets, milled or cutfibers, and other forms of the polymers. These polymeric materials donot participate in the polymeric binder resin. Preferred fillers includetitanium dioxide, mica, talc, vinyl rubber, nylon, rayon, polyesters,graphite, and mixtures thereof.

The amount of filler in the coating composition typically depends on thedesired properties of the composition. These properties may include thestrength, flexibility, ultraviolet radiation resistance, chemicalresistance, permeability, and cost of the coating composition. Oftenmore than one type of filler is used. A combination of fillers mayprovide desired advantages for the coating composition and/or overcomedisadvantages arising from other components in the film. Typically, theamount of filler ranges from 0 to about 600 phr, preferably about 10 to150 phr, more preferably, about 20 to 100 phr, and most preferably about25 to 80 phr, based on 100 parts by weight of the polymeric binderresin. Larger amounts of filler may also be used. However, if the amountof filler is too large then the polymeric binder resin may not besufficient to hold together the film formed from the coatingcomposition.

In some embodiments, the coating composition contains about 5 to 60 phr,and preferably about 20 to 50 phr, of a polymeric filler material, suchas vinyl rubber, nylon, polyester, rayon, or combinations thereof. Thesepolymeric filler materials often enhance the sprayability andwearability of the resulting coating compositions and films.

In some embodiments, the coating composition contains about 0.1 to 20phr, and preferably about 5 to 15 phr, of a metallic oxide. Thepreferred metallic oxide is titanium dioxide.

In addition, some embodiments contain about 1 to 35 phr, and preferablyabout 5 to 25 phr, of a silicate, such as mica. Mica has been found tobe particularly useful in reducing the size and number of pinholes.

The coating composition may optionally include a pigment or dye. Thepigment or dye may impart a desired color to the coating composition andmay be added for aesthetic purposes. The pigment or dye may also beincluded in the coating composition to, for example, aid the user indetermining which portion of a surface has been covered by the coatingcomposition. The pigment or dye may also absorb light which can harm thefilm. For example, the pigment or dye may absorb one or more wavelengthsof ultraviolet (UV) light.

Pigments and dyes may be powders, lakes, metal flakes, organic ororganometallic molecules, and the like. Examples of suitable pigmentsand dyes include iron lakes, iron oxide, such a red, yellow, and blackiron oxides, other metal oxides, and carbon black. Typically, 0 to about10 phr, and preferably about 0.1 to 3 phr, of pigment or dye is used.However, larger amounts may be used. In addition to compounds usedprimarily as pigments or dyes, the coating composition may also includeother components, such as the filler material, that also act as apigment or dye. For example, titanium dioxide which may also be afiller, is a pigment. In such cases, the amount of the filler/pigment(e.g., titanium dioxide) in the coating composition may berepresentative of that described above for the filler material.

Another optional additive is an antioxidant. Polymers with styrene anddiene monomer units are unsaturated and are susceptible to attack byoxygen. An antioxidant may be added to the coating composition toprevent the oxidation of the polymers in the polymeric binder resin. Insome commercial polymers, an antioxidant is already provided with thepolymer and additional antioxidant may not be needed. For example,commercial styrene-containing and diene-containing polymers, includingthe Kraton® Series D 1100 and G 1600 polymers, already have an amount ofantioxidant added to the polymer to facilitate manufacturing, shipping,and storage. However, additional antioxidant may be added as desired orneeded.

A variety of antioxidants are known and may be included in the coatingcomposition. One suitable type of antioxidant includes a substitutedphenolic compound. Commercial antioxidants of this type include Irganox®1010 and 565 (Ciba-Geigy Co., Ardsley, N.Y.), Ethanox® 330 (Ethyl Corp.,Baton Rouge, La.), and BHT (butylated hydroxytoluene, available from avariety of sources). Other types of antioxidants may also be used.

The amount of antioxidant in the coating composition ranges from 0 toabout 10 phr. If an antioxidant is used in the coating composition, theamount of antioxidant preferably range from about 0.01 to 5 phr, andmore preferably from about 0.05 to 2 phr.

The coating composition may also include an ultraviolet (UV) absorber orblocker. This may be particularly useful in coating compositions thatare exposed to sunlight or other sources of ultraviolet light. Examplesof suitable UV absorbers or blockers include substituted benzotriazoles,hindered amines, benzophenones, and monobenzoates. Commercial UVabsorbers or blockers include Tinuvin® P/300 Series and Tinuvin® 770from Ciba-Geigy Co. (Ardsley, N.Y.), Cyasorb® UV 531 from AmericanCyanamid (Wayne, N.J.), and Eastman® RMB from Eastman Chemical Co.(Kingsport, Tenn.). Other types of UV absorbers or blockers may also beused.

The amount of UV absorber or blocker in the coating composition rangesfrom 0 to about 10 phr. If an UV absorber or blocker is used in thecoating composition, the amount of UV absorber or blocker preferablyrange from about 0.01 to 5 phr, and more preferably from about 0.05 to 2phr.

Ozone blockers may also be used, particularly for coating substratesthat will be exposed to air or to ozone-forming devices. Examples ofozone blockers include dibutyl thiourea, nickel dibutyl-dithiocarbomate(DuPont, Wilmington, Del.), Ozone Protector 80 (Reichhold Chemicals,Durham, N.C.) and the like. The amount of ozone blocker in the coatingcomposition ranges from 0 to about 10 phr. If an ozone blocker is usedin the coating composition, the amount of ozone blocker preferably rangefrom about 0.01 to 5 phr, and more preferably from about 0.05 to 2 phr.

The coating composition may also include a plasticizer. The plasticizermay increase the toughness and flexibility of the film resulting fromthe coating composition. In many cases, a plasticizer is not needed asthe combination of the polymers in the polymeric binder resin plasticizeeach other. However, when desired or needed an additional plasticizermay be added. Examples of useful plasticizers include butyl stearate,dibutyl maleate, dibutyl phthalate, dibutyl sebecate, diethyl malonate,dimethyl phthalate, dioctyl adipate, dioctyl phthalate, butyl benzylphthalate, benzyl phthalate, octyl benzyl phthalate, ethyl cinnamate,methyl oleate, tricresyl phosphate, trimethyl phosphate, tributylphosphate, trioctyl adipate and the like. Other plasticizers are known.

Typically, the coating composition includes 0 to about 50 phr ofplasticizer. For those embodiments that use a plasticizer, the preferredamount ranges from about 5 to 40 phr, more preferred from about 7 to 30phr, and most preferred from about 10 to 20 phr. The amount ofplasticizer used in the coating composition depends, at least in part,on the desired properties and the composition of the polymeric binderresin. Typically, the more plasticizer, the more elastic the film,however, if the amount of plasticizer is too great than the cohesivenessof the film resulting from the coating composition may decrease. Aplasticizer may be particularly useful in combination with highstyrene-content polymers.

Other components may be used in the coating composition. For example, ithas been found that the addition of a small amount (less than 0.1 phr)of colloidal silica (e.g., Cab-O-Sil® M-5 or TS-610, Cabot Corp.,Tuscola, Ill.), particularly in combination with about 1 to 10 phr ofmineral spirits, causes the volume of the coating composition and theresulting film to increase. Examples of other optional components of thecoating composition includes for example, perfumes, deodorants, foamingagents and tackifiers (e.g., Wingtack® series tackifiers from GoodyearTire & Rubber Co., Akron, Ohio).

Preparation Methods

The coating composition is prepared by combining the organic solventwith the other components, including the polymers, the hydrocarbonresin, and the optional filler, pigment, antioxidant, plasticizer, andany of the other optional components. This combination is then mixed todissolve and/or disperse the components within the solvent and form thecoating composition. The mixing continues for about 30 minutes to 2hours or until the coating composition appears creamy and the particlesin the coating composition appear uniform as viewed through a fallingfilm of the coating composition.

Various modifications can be made to this procedure. In someembodiments, the polyolefin polymer is not added until after the mixingof the solvent and the other components begins, particularly if thepolyolefin polymer is a polybutene polymer (e.g., polybutylene orpolyisobutylene). Polyolefin polymers, particularly polybutylene andpolyisobutylene, often do not disperse well in the solvent unless thepolyolefin polymer has been previously liquefied by dissolving ordispersing in a solvent, such as mineral spirits, and/or by heating. Thepolyolefin polymer may be added into the solvent mixture over a periodof time, for example, over a period of 10 minutes or less. Preferably,the polyolefin polymer is heated to a temperature ranging from about 90to 125° C. and mixed with mineral spirits prior to being poured into thesolvent mixture, as this typically enhances dispersion of the polyolefinin the solvent.

Furthermore, for those embodiments which have vinyl rubber as a fillercomponent, it may be desirable to allow the vinyl rubber to sit in aportion of the organic solvent for fifteen minutes to 2 hours until thevinyl rubber and the organic solvent form a paste. This paste istypically added to the mixture with the rest of the components before orshortly after adding the solvent. The formation of a paste facilitatesthe dispersal of the vinyl rubber filler throughout the coatingcomposition.

Application

The coating composition can be applied by a variety of techniques,including, for example, rolling, brushing, spraying, squeezing,backrolling, pouring, troweling, or otherwise coating the surface of thesubstrate. A preferred application technique is spraying the coating onthe substrate. Combinations of these techniques may also be usedincluding spraying the coating composition on the structural unit andthen rolling or brushing the sprayed coating composition to obtain amore uniform coating. The coating composition may be used on bothinterior and exterior surfaces of structures, as well as on othersurfaces that need to be waterproofed.

Spraying the coating composition on the substrate requires a flowablecoating composition. Many physical properties affect flowability, suchas, for example, viscosity, temperature, and the like. Usually, as theviscosity is lowered, the easier it is to spray the coating composition.Normally as the temperature of the material rises, the easier it is tospray the coating composition. Coating compositions applied in coldclimate areas typically require special attention to maintain theflowability of the composition.

The thickness of the coating will often depend on the particular surfaceand material of the structural unit, as well as the projected exposureto moisture. Rougher surfaces and surfaces in areas with more moisturemay require a thicker coating. In addition, thicker coatings may be usedin situations where the coating may be subject to puncturing. Forexample, a coating on the exterior of a below-grade masonry unit, suchas a foundation, should be thick enough to withstand bridging cracksthat develop in the substrate and the backfilling process. Typical drycoating thickness range from about 5 to 100 mil (about 125 to 2500 μm),and preferably from about 40 to 60 mil (about 1000 to 1525 μm). Thickerand thinner coatings may also be used depending, in part, on the desireduse of the structural unit.

Upon drying, the coating composition becomes a film. Typical dryingtimes range from 4 to 24 hours. Longer or shorter drying times may beused depending on the thickness of the applied coating composition, theair temperature and humidity and the desired amount of solvent thatshould be removed.

The coating composition of the present invention may be applied byitself or in conjunction with another waterproofing system. For example,the coating composition of the present invention may be coated on astructural unit, followed by the application of waterproofing sheeting.In addition, the coating composition of the present invention may beused with another coating to provide enhanced protection. A preferredcoating for use with the coating of the present invention is ahard-film-forming composition, such as, for example, the compositionsdescribed in U.S. Pat. No. 5,482,737 incorporated by reference herein.In one embodiment, the hard-film-forming composition includes an organicsolvent and a polymeric binder resin. The polymeric binder resincontains at least 85 wt. % of a polymer or combination of polymershaving at least 75 wt. % styrene monomer units. Such polymers includepolystyrene homopolymer and copolymers of polystyrene with diene,olefin, acrylate, and acrylonitryl monomer units, such as high impact ormedium impact polystyrene. The preferred combination of the two coatingcompositions includes applying the coating composition of the presentinvention over the other coating. The coating composition of the presentinvention may, at least in some cases, be applied over the other coatingbefore the other coating is completely dry.

EXAMPLES

The following examples further illustrate the invention. These examplesare merely illustrative of the invention and do not limit the scope ofthe invention.

Between one quart and several gallons of each of the coatingcompositions (Table 1 labeled A-G) were prepared using the followingmaterials and amounts:

TABLE 1 Materials and Amounts for the Coating Compositions A B C D E F G(kg) (kg) (kg) (kg) (kg) (kg) (kg) Methylene Chloride 0.5 0.3 Xylene1.43 1.81 1.96 2.00 1.58 0.5 0.7 Mineral Spirits 0.46 Nevex ® 100 0.290.43 0.40 0.40 0.21 1.5 2.5 (Coumarone-indene resin) Kraton ® 1102 0.320.50 0.38 0.36 0.57 1.5 0.5 (S-B-S polymer) Kraton ® 1107 0.43 0.59 0.430.42 0.50 (S-I-S polymer) Kraton ® 1650 0.23 0.25 0.25 0.25 (S-EB-Spolymer) Vantack ® 85 0.40 Talc 0.66 Titanium Dioxide 0.05 0.07 0.040.03 0.04

Many of the components used in the Examples were available from avariety of manufacturers and distributors. For example, the Nevex 100®hydrocarbon resins were available from Neville Chemical Company(Pittsburgh, Pa.). The Kraton® polymers were available from ShellChemical Company (Houston, Tex.). Vantack® 85 is available fromVanderbilt Chemical Company (Norwalk, Conn.). Talc, titanium dioxide,xylene, methylene chloride, and mineral spirits were available from avariety of manufacturers.

The polymers, hydrocarbon resin and titanium dioxide, were combined in avessel. The solvent (xylene and optionally mineral spirits) was thenadded. The solvent and other components were mixed for 20 to 45 minutes.The mixing continued until the mixture appeared creamy and the particlesin the mixture appeared uniform when viewed through a falling film ofthe mixture.

Each coating was sprayed or brushed onto the substrate.

Each coating composition was allowed to dry on a substrate, such as amasonry block. The resulting films were solid with a minimum ofpinholing and had elastomeric qualities.

TABLE 2 Materials and Amounts for Coating Compositions H I (kg) (kg)Xylene 1.95 1.86 Nevex ® 100 0.73 0.00 (Coumarone-indene resin) Kraton ®1101 (S-B-S polymer) 0.86 Kraton ® 1102 (S-B-S polymer) 0.44 0.33Kraton ® 1107 (S-I-S polymer) 0.20 Clay 0.47 Titanium Dioxide 0.09 0.09Talc 0.34

Formula H shown in Table 2 illustrates another example of the inventioncomposition and is used in the viscosity tests that follow (Tables 3a,3b and 3c). Formula I shown in Table 2 illustrates a coating compositionwithout hydrocarbon resin used in the viscosity tests that follow(Tables 4a, 4b, and 4c).

TABLE 3a Brookfield Viscosity Results Formula H Shear Shear Speed TorqueViscosity Stress Rate Temp Time Item # RPM % mPas N/m² l/s ° C. MM:SS 12.5 14.3 14300 12.2 0.85 −9.6 04:02 2 5.0 25.7 12850 21.8 1.70 −9.602:00 3 10 47.6 11900 40.5 3.40 −9.6 01:00 4 20 89.8 11225 76.3 6.80−9.6 00:30 5 10 46.5 11625 39.5 3.40 −9.6 01:00 6 5.0 24.6 12300 20.91.70 −9.6 02:00 7 2.5 13.7 13700 12.2 0.85 −9.6 04:00

TABLE 3b Brookfield Viscosity Results Formula H Shear Shear Speed TorqueViscosity Stress Rate Temp Time Item # RPM % mPas N/m² l/s ° C. MM:SS 12.5 13.5 13500 11.5 0.85 −0.3 04:01 2 5.0 20.6 10300 17.5 1.70 −0.301:59 3 10 34.0  8500 28.9 3.40 −0.3 01:00 4 20 59.8  7475 50.8 6.80−0.4 00:30 5 10 32.9  8225 28.0 3.40 −0.4 01:00 6 5.0 19.8  9900 16.81.70 −0.4 02:00 7 2.5 13.0 13000 11.1 0.85 −0.4 04:00

TABLE 3c Brookfield Viscosity Results Formula H Shear Shear Speed TorqueViscosity Stress Rate Temp Time Item # RPM % mPas N/m² l/s ° C. MM:SS 12.5 15.5 15500 13.2 0.85 11.6 04:01 2 5.0 20.5 10250 17.4 1.70 11.702:00 3 10 29.1  7275 24.7 3.40 11.7 01:00 4 20 44.5  5563 37.8 6.8011.7 00:30 5 10 28.9  7225 24.6 3.40 11.7 01:00 6 5.0 20.1 10050 17.11.70 11.6 02:00 7 2.5 14.9 14900 12.7 0.85 11.6 04:00

TABLE 4a Brookfield Viscosity Results Formula I Shear Shear Speed TorqueViscosity Stress Rate Temp Time Item # RPM % mPas N/m² l/s ° C. MM:SS 12.5 89.2 89200 75.8 0.85 30.2 03:42 2 5.0 * * * 1.70 30.4 01:59 310 * * * 3.40 30.4 01:00 4 20 * * * 6.80 30.5 00:30 5 10 * * * 3.40 30.601:00 6 5.0 * * * 1.70 30.7 02:00 7 2.5 90.6 90600 77.0 0.85 31.104:00 * indicates a value too high for the instrument to read

TABLE 4b Brookfield Viscosity Results Formula I Shear Shear Speed TorqueViscosity Stress Rate Temp Time Item # RPM % mPas N/m² l/s ° C. MM:SS 12.5 99.7 99700 84.7 0.85 26.5 04:01 2 5.0 * * * 1.70 26.5 01:59 310 * * * 3.40 26.5 01:00 4 20 * * * 6.80 26.5 00:30 5 10 * * * 3.40 26.601:00 6 5.0 * * * 1.70 26.6 02:00 7 2.5 99.6 99600 84.7 0.85 26.504:00 * indicates a value too high for the instrument to read

TABLE 4c Brookfield Viscosity Results Formula I Shear Shear Speed TorqueViscosity Stress Rate Temp Time Item # RPM % mPas N/m² l/s ° C. MM:SS 12.5 * * * 0.85 10.5 04:03 2 5.0 * * * 1.70 10.6 02:00 3 10 * * * 3.4010.6 01:00 4 20 * * * 6.80 10.6 00:30 5 10 * * * 3.40 10.7 01:00 65.0 * * * 1.70 10.7 02:00 7 2.5 * * * 0.85 10.7 04:00 * indicates avalue too high for the instrument to read

The present invention should not be limited to the particular examplesdescribed above, but rather should be understood to cover all aspects ofthe invention as fairly set out in the attached claims. Variousmodifications, equivalent processes, as well as numerous structures towhich the present invention may be applicable will be readily apparentto those of skill in the art to which the present invention is directedupon review of the instant specification.

I claim:
 1. A waterproofing composition, comprising: about 33 phr toabout 250 phr of an organic solvent; about 10 phr to about 50 phr of apolyindene; about 50 phr to about 90 phr of a polymer selected from thegroup consisting of a polymer having olefin monomer units, a copolymerhaving styrene and olefin monomer units with a styrene-content of about10 wt. % to about 60 wt. % and mixtures thereof; and a polymer havingstyrene monomer units and a styrene content of 60 wt. % or greater. 2.The waterproofing composition of claim 1, wherein the polymer havingstyrene and olefin monomer units is selected from the group consistingof a styrene-diene-styrene block copolymer, astyrene-ethylene-butylene-styrene block copolymer and mixtures thereof.3. The waterproofing composition of claim 1, further comprising about 20phr to about 600 phr of a filler.
 4. A waterproofing composition,comprising: about 33 phr to about 250 phr of an organic solvent; about10 phr to about 50 phr of a polyindene; about 50 phr to about 90 phr ofa polymer having styrene and olefin monomer units with a styrene contentof about 10 wt. % to about 60 wt. % and a polyolefin homopolymer.
 5. Thewaterproofing composition of claim 4, wherein the polymer having styreneand olefin monomer units is selected from the group consisting of astyrene-diene-styrene block copolymer, astyrene-ethylene-butylene-styrene block copolymer and mixtures thereof.6. The waterproofing composition of claim 4, wherein the compositionfurther comprises a polymer having styrene monomer units and a styrenecontent of 60 wt % or greater.